Fluorocarbon compounds and polymers thereof



United States Patent 3,457,247 FLUOROCARBON COMPOUNDS AND POLYMERSTHEREOF Atsuo Katsushima, Fuse-shi, Iwao Hisamoto, Suita-shi,

and Shoshin Fukui, Takahisa Kato, and Masayuki Nagai, Mishima-gun,Osaka-fu, Japan, assignors to Daikin Kogyo Kabushiki Kaisha, Kitaku,Osaka-shi, Japan, a

juridical person of Japan No Drawing. Filed Feb. 8, 1966, Ser. No.525,848 Claims priority, application Japan, Feb. 12, 1965, 40/7,926,40/7,928, 40/7,929; Mar. 24, 1965, 40/ 17,328 v Int. Cl. C08f 3/66,-D06m 15/36 US. Cl. 260-895 Claims ABSTRACT OF THE DISCLOSURE Newcompounds having the general formula:

wherein R9, R3, R3, and R are respectively one member of the groupconsisting of F, -CF CF CF C F; 0 F3 -o F 0 F 0 F C F 0 Fa and c F 0 r;

with the proviso that R and R8 are not both F and 3,457,247 PatentedJuly 22, 1969 l (Formula 4), with unsaturated aliphatic acids or deriva-R? and Rf are not both F; R R and R are respectively one member of thegroup consisting of H and -CH and n is an integer of from 0 to 10.

This invention relates to a new and useful class of fluorocarboncompounds and their polymers; and to aqueous emulsions or organicsolvent solutions thereof suitable for treating solid materials, suchas, fibrous or porous materials to render them waterand oil-repellent.

The new compounds are esters having the general formula:

wherein R R3, R9 and Rf represent respectitvely F, 3,

except the case of both R; and R? or both R? and R; being F; R R and Rrepresent respectively ---H or CH and n is an integer of from 0 to 10.

tives thereof having the formula CHFCH (CH COY (Formula 5), as shown inthe following equations:

wherein R R8, R3, R5 R R R and n are as defined before; and Y is aholgene, OH or OR R being a lower alkyl of 1 to 5 carbon atoms. Therepresentative examples .of the starting perfiuoroolefin of Formula 3are hexafluoropropylene dimers and trimers which are prepared byorigomerization of hexafluoropropylene, and which are shown as follows;

0 F 0 Fa-C=C F- C 13-0 F;

0 Fa-C 1 0 r=o r-o Fa 0 Fa 0 Fa C F3-C F-C F3 CF; 0 F3-C FQF=(137O'F-CF3 CF3-C=G F- F- F F3 (11F: The aliphatic alcohols of Formula .4.employed in the process-I of said equations include methanol, ethanoland isopropanol, most desirable. being methanol. The process-Icomprising the addition reaction of said perfiuoroolefins The esters ofthis invention can be readily polymerized to produce solid polymerswhich are of hydrophobic and oleophobic property and available aswaterand oil-repellent agents. 7

Said esters of the invention can be prepared by esterify- I andaliphatic alcohols may be usually carried out in a closed vessel such asglass ampoule, stainless-steel autoclave, etc., in the presence offree-radical catalysts such as benzoyl peroxide, tertiarybutylhydroperoxide, ditertiarybutyl peroxide, tertiarybutyl perbenzoate,diisopropyl peroxydicarbonate, azobisisobutyronitrile, etc. The suitablereaction temperature is selected from a wide range according to thekinds of the catalysts employed, but a temperature of 40 to 1500 C. isusually preferred. The reaction pressure may be about 0 to 10 kg./cm;g., although an autogenous pressure is used and preferred in many cases.The reaction is accelerated or facilitated by applicating vigorousagitation and/or by adding to the reaction system organic liquids suchas trichlorotrilluoroethane which are solvents for both startingreactants and inert to the 3 reactants and the products. The amount ofthe starting alcohol, based on the amount of perfluoroolefin employed,may be selected from a wide range, but in general it is desirable that aslight excess of the alcohol is employed. The starting perfluoroolefinsmay be employed either singly or in admixture, and the latter casesometimes accelerates =the addition reaction. For instance, whenhexafiuoropropylene dimer and trimer are employed in admixture with eachother, the addition of aliphatic alcohol to the trimer is accelerated.It is accordingly no need to separate dimer and trimer respectively fromhexafluoropropylene origomer.

The second process-II comprises the esterification of the adducts,w-hydropolyfluoroalkanols of Formula 2, resulting from the aforesaidfirst process-I with unsaturated aliphatic acids or their derivatives ofFormula 5. Of the compounds of Formula 5, particularly those in which nrepresents zero, e.g. acrylic acid or methacrylic acid or an acidchloride thereof is preferably employed. The esterification may heusually carried out at an elevated temperature, preferably at about 50to 150 C. The reaction pressure is not critical, but an autogenouspressure is usually preferred. The amounts of the reactants to beemployed may be selected from a wide range, although the startingcompound of lower boiling point is desirably employed in a theoreticalor slightly excess amount. A dehydrogenating agent, such as,concentrated sulfuric acid, dried hydrogenchloride gas, etc., may beadded to the reaction system if acid is employed as an esterifyingagent, and a hydrogenhalide acceptor, such as, zinc chloride,concentrated sulfuric acid, pyridine, quinoline, etc., may be added ifacid halide is employed. One or more species of polymerizationinhibitors, such as, copper powders, hydroquinone, amines, etc., may bealso added to the reaction system so as to prevent the polymerization ofthe starting unsaturated compounds and the resultant compounds.

The desired esters of this invention can be separated from the resultantreaction mixtures by the conventional methods such as rectification ofsaid mixture containing polymerization inhibitors which have been addedbefore or after the reaction, as required.

The typical examples of the present esters are as follows:

F F CH3 tions. Said esters are polymerized either singly or in admixturewith each other or with copolymerizable monomers of other kinds whichcontain an ethylenic linkage in the molecules, to produce novelhomopolymers or copolymers of this invention.

Said copolymerizable monomers include (1) acrylic acid, methacrylic acidor such esters thereof as methyl, ethyl, butyl, isobutyl, propyl,Z-ethylhexyl, hexyl, decyl, lauryl, stearyl, etc.; (2) vinyl esters ofaliphatic acids such as vinyl acetate, vinyl propionate, vinylcaprylate, vinyl laurate, vinyl stearate, etc.; (3) styrene or styrenederivatives such as u-methylstyrene, p-methylstyrene, etc.; (4)halogenated vinyl or halogenated vinylidene compounds such as vinylfluoride, vinyl chloride, vinyl bromide, vinylidene fluoride, vinylidenechloride, etc.; (5) allyl esters of aliphatic acids such as allylheptanoate, allyl caproate, allyl caprylate, etc.; (6) alkylvinylketones such as methylvinyl ketone, ethylvinyl ketone, etc.; (7)acrylamides such as N-methyl acrylamide, N-methylol acrylamide, glycidylacrylate, glycidyl methacrylate, etc.; (8) diene compounds such asbutadiene, 2,3-dichloro-1,3- butadiene, isoprene, etc.; and (9)fluorinated unsaturated esters such as R (CH OOCCR=CH R CH=CH (CHOOCCR=CH (wherein R, is perfluoroalkyl of 3 to 21 carbon atoms, R ishydrogen or methyl, and q is an integer of from 1 to 10), etc. Thecopolymer comprising 99 to 25 weight percent of the present monomer and1 to 75 weight percent of the comonomer containing no fluorine in themolecule, (1) to (8) above, exhibits sufficient waterand oilrepellency,although the copolymer containing less than 25 weight percent of thepresent monomers exhibits poor or no waterand oil-repellency.

Of polymerization methods as stated before, the most desirable one is anemulsion polymerization for which a conventional technique used in theemulsion polymerization of vinyl compounds is applicable. For instance,one or more species of the present monomers to be polymerized aredispersed in an aqueous medium having dissolved therein dispersants andfree-radical catalysts, if necessary, and polymerized. The dispersantsemployed include those compounds being anionic, cationic or non-ionicsurfactant. The desirable anionic surfactant is a sodium salt ofsulfated alkenyl (C to C acetate, sodium oleate, sodium salt of sulfatedmethyloleate, an ammonium w-hydropolyfluoroalkanoate (C to C an ammoniumperfiuoroalkanoate (C to C a sodium alkyl (C to C sulfate, a sodiumalkyl (C to C naphthalene, a sodium alkyl (C to C18) naphthalenesulfonate, etc. The desirable cationic surfactant is(dodecylmethylbenzyl)-trimethylammonium chloride,benzyldodecyl-dimethylammonium chloride,N-(2-(diethylamino)-ethyl)-oleamide hydrochloride, dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, etc. Thedesirable non-ionic surfactant is a condensation product ofpolyoxyethylene glycol and hexyl phenol, isooctyl phenol, hexadecanol,oleic acid, alkane (C to C thiol, alkyl (C to C amine.

The free-radical catalysts employed include those compounds known to theart for the polymerization of conventional vinyl compounds, for example,benzoyl peroxide, lauroyl peroxide, tertiarybutyl perbenzoate,l-hydroxycyclohexylhydro peroxide, 3-carboxypropionyl peroxide, acetylperoxide, azobisisobutyramidine dihydrochloride, azobisisobutyronitrile,sodium peroxide, barium peroxide, hydrogen peroxide, potassiumpersulfate, ammonium persulfate, etc.

The polymerization temperature varies over a wide range according to thepolymerization method and the kinds of monomers, dispersants andcatalysts employed, but in emulsion polymerization a temperature of from0 to 80 C. is usually employed, although 20 to 70 C. is preferred. Thepressure, 0 to 10 kg./cm. g. is usually 6 applied in emulsionpolymerization, most desirable being 0 to 5 kg./cm. g.

The polymers of this invention, including both homopolymers andcopolymers are characterized by the presence of the skeletal chain ofrecurring or repetitive w-hydropolyfluoroalkyl ester units which can berepresented as follows:

wherein R RE, RE, R5, R R R and n are as defined before. Thehomopolymers contain these recurring units attached to one another bythe valence bonds shown in the above formula, and the copolymers containthese groups interspersed with groups derived from copolymerizablemonomers employed.

These polymers of this invention have a markedly excellentwater-repellent and oil-repellent property due to a multiplicity ofw-hydroperfluoro alkyl group (O-CH) Rf R and have a good aifinity forfibrous or other porous materials to be treated therewith.

In general it has been considered that a fluorocarbon polymer havinghydrogen atom at w-POSitiOn of the fluoroalkyl group cannot impartsufiicient oil-repellency to the materials treated therewith. Forinstance, the cotton fabrics treated with a polymer of H 1 CH O O whichis known as waterand oil-repellent are wetted by the drops of a 6:4volume ratio mixture of Nujol (white mineral oil) and n-heptane,although they repel a 7:3 volume ratio mixture of Nujol and n-heptane.

On the other hand polymers of this invention always display excellentoil-repellent effects for example, the cotton fabrics treated with thepolymer of the present ester having only 6 carbon atoms bonded tofluorine can repel even a 4: 6 volume ratio mixture of Nujol andn-heptane.

It is easily understood by one skilled in the art that these specificcharacteristics of the present polymers make them especially suitablefor the use of waterand/ or oilrepellent.

Waterand oil-repellent compositions containing the present polymers areof various forms, such as aqueous emulsions, organic solvent solutionsor self-pressurized sprayable products, aerosols. As aqueous emulsionprepared by emulsion polymerization may be advantageously used as it is,or may be diluted or concentrated. There may be added stabilizers, pHadjusters and/or other wateror oil-repellent compounds known to the art,where necessary. The aqueous emulsion can be also prepared by dispersingthe polymer powder in an aqueous medium. An organic solvent solution isprepared by dissolving the polymer at an atmospheric or elevatedtemperature in one or more of such organic solvents as acetone and/ortrichlorotrifiuoroethane etc. In preparation of aerosols, a propellantsuch as dichlorodifluoromethane, monofiuorotrichloromethane,dichlorotetrafiuoroethane, etc., is added to such a solution.

The waterand oil-repellent compositions of this invention may be appliedto the solid materials by painting, dipping or spraying at roomtemperatures, or at elevated temperatures conventional in the art. Thematerials to be treated include fibrous or other porous or non-porousmaterials such as woven fabrics, knit fabrics, papers, fibreboards,felts, etc., made of natural fibres such as cellulose, cotton, wool,etc., fully synthetic fibres such as polyamides, polyesters,polyacrylonitrls, etc. and/or partially synthetic fibres such ascellulose acetate, cellulose propionate, etc.; leathers; and goods madeof glass, woods, etc.

The coated materials thus obtained are dried at room temperatures or atelevated temperatures and further, if necessary, a curing process may beapplied. During or after the curing, a soaping process may also beapplied, as required. The drying may be accomplished or accelerated bythe application of mild heating (usually 80 to 150 C.), a current of airor other inert gas, reduced pressure or by a combination of such means.The curing process is usually required if emulsion-type compositions areused, whereby the polymer particles coalesce each other to form acontinuous polymer layer firmly attached to the coated materials. Saidprocess is carried out by heating the materials at 80 to 200 0,preferably at 100 to 150 C., for 1 to 20 minutes. The soaping process isalso required in using emulsion-type compositions, if necessary, wherebydispersants and polymerization initiators contained in emulsions arewashed out. Said process is usually carried out by washing the materialswith a 0.1 to 0.5 weight percent aqueous solution of a neutral detergentat 40 to 60 C. for 10 seconds to 5 minutes. There is no need, as a rule,to apply said curing and soaping processes, if solution-type oraerosol-type compositions are used.

Aforementioned treating methods are illustrative only and we do notintend to limit this invention to the same, as there are various othermodifications which are readily apparent to those skilled in the art.

The thus treated materials, which are coated with the polymers of thisinvention, display a markedly excellent waterand oil-repellent propertydue to the w-hydroperfluoroalkyl side chain as n exposed on the outersurface of the treated materials. For instance, drops of water or oildeposited on the surface will remain or run off rather than spreadingand wetting the surface. This excellent waterand oil-repellent propertyis secured when the polymer of this invention is attached to thematerials in the range of only from 0.1 to 5 weight percent based on theweight of the materials, although said waterand oil-repellent propertywill increase if a greater amount of polymer is attached.

The waterand oil-repellent compositions of the invention may be alsoemployed with other known waterrepellent and/or oil-repellent agents,whereby the treated materials increase in waterand/ or oil-repellenteffects and in particularly durability for washing and dry-cleaning inmany cases. The most desirable known agents are quaternary pyridiniumsalts having a higher alkyl group of 12 to carbon atoms. For instancethere are exemplified compounds having the formula of etc. which areknown to the art as a water-repellent agent and available under thetrade name Norane R (trademark of Warwick Chemical Co., U.S.A.), ZelanAP (trademark of E. I. du Pont de Nemours & Co., U.S.A.) and Velan PF(trademark of Imperial Chemical Industries Ltd., U.K.).

The treatment with the known waterand/or oilrepellent agents ispreferably applicable before or after the treatment with the presentcompositions by two-step treatment, although it is also applicableduring the treatment with the present compositions by one-steptreatment.

EXAMPLE 1 A IOO-cc. glass ampule was charged with 32 grams of methanol,1 gram of benzoyl peroxide and 75 grams of a mixture of 2 species ofhexafluoropropylene dimers, i.e.,

CF30]? CF20 F 0 F and C F;(]1=C F-o F20 F OF; C F:

obtained by heating hexafiuoropropylene in the presence of potassiumbromide in dimethyl formamide at C. for 1 hour. Then the mixture wascooled and solidified with liquid air, and the air in the ampule wasevacuated by a vacuum pump and nitrogen gas was substituted, and thenthe nitrogen gas was again evacuated by the vacuum pump and the ampulewas sealed under a reduced pressure. The reaction system was heated withviolent shaking at 100 C. for 10 hours, and on completion of thereaction a homogeneous solution was obtained. The resultant solution wasrectified to obtain 59 grams of a distillate boiling at -l42 C. Bypreparative gas chromatograph the distillate was divided into 2components. Said 2 components were confirmed by infrared spectroscopicanalysis and elementary analysis to be addition products of methanol tothe starting hexafluoropropylene dimers, namely,

Then, 48 grams of the mixture of the fiuorinated alcohols synthesized asabove and 0.3 gram of hydroquinone and 0.3 gram of copper powder wereplaced in a 100-cc., 4-necked flask with a reflux cooler, thermometer,nitrogen gas injector and dropping funnel and the air in the flask wasthoroughly replaced by nitrogen gas, and heated to 60-70" C. withviolent agitation, during which 15 grams of acrylchloride was addeddropWise thereto in about 30 minutes, after which the reaction wascontinued for about 1 hour. The resultant mixture was rectified underreduced pressure, yielding 2 grams of byproduct of a low boiling pointand 15 grams of a distillate (A) boiling at 798l C./2022 mm. Hg and 24grams of a distillate (B) boiling at 86-87 C./2022 mm. Hg. Bothdistillates (A) and (B) above showed absorptions, by infrared spectroscopic analysis, at 5.7 due to C=O, at 1.15 4 due to CH=CH and at7-9.5 due to C-F.

Elementary analysis gave:

Substance (A)C=30.9%; F=58.7%; H=1.61%. Substance (B)C=32.1%; F=58.0%;H=1.50%.

Calculated values for C F H O :C=3l.l%; F: 59.1%; H=1.55%.

Thus the substances (A) and (B) were confirmed respectively to be theesters of the starting fiuorinated alcohols and acrylchloride, andfurther by nuclear magnetic resonance analysis to be:

CF3 CF3 Substance (B): C Fz-(L F-O FH(|) FC H3OCC H=C H:

l! A mixture of 6 grams of the substance (A) and 9 grams of thesubstance (B) above, 90 grams of deoxidated water, 7 grams of acetoneand 3.5 grams of CF (CF COONH temperature. Agitation was furthercontinued for 5 hours and 40 minutes at 55 to 60 C., whereby 161 gramsof a stable polymer dispersion having a concentration of 8.9 weightpercent was obtained.

The resultant dispersion was diluted with water to a polymerconcentration of 1.0 Weight percent and a cotton gauze, 30 cm. x 45 cm.,was immersed into the diluted dispersion. Then the gauze was dried inthe air and further dried in a drier at 130 C. for 15 minutes. The driedgauze was washed with a 0.3 weight percent aqueous solution of a neutraldetergent and thoroughly washed with water.

The gauze thus treated showed no change in touch, brightness, strength,etc., and exhibited excellent waterrepellency and oil-repellencyrepelling a 1:1 volume ratio mixture of liquid paraffin and n-heptane.

EXAMPLE 2 A 600-cc. stainless steel autoclave was charged with 270 gramsof the mixture of 3 species of hexafluoropropylene trimers, i.e.,

which were synthesized in the manner as Example 1, 40 grams of methanol,300 grams of trichlorotrifiuoroethane and 4 grams ofditertiarybutylperoxide and the air in the autoclave was thoroughlyreplaced by nitrogen gas, and the system was heated with shaking at 130C. for 30 hours, producing a homogeneous solution. The solution wasrectified whereby 106 grams of the unreacted trimers was recovered and95 grams of a distillate (A) boiling at 7581 C./1011 mm. Hg, 26 grams ofa distillate (B) boiling at 8485 C./10-1l mm. Hg and 35 grams of adistillate (C) boiling at 90-91 C./1011 mm. Hg were obtained.

These distillates (A), (B) and (C) respectively showed an broadabsorption near 3.0;1. due to OH, and the following values were obtainedby elementary analysis: Substance (A)C=24.5%; F=71.2%; H=0.90%.Substance (B)C=24.7%; F=70.8%; H=0.85%. Substance (C)C=24.7%; F=70.3%;H=0.86%.

Calculated values for C F H O: C=24.90%; F: 70.95%; H:O.83%.

Thus these 3 substances (A), (B) and (C) were found respectively to be 3isomers, and further by nuclearmagnetic resonance absorption analysiswere found that:

F3 F3 Substance (A): C FsC FCIIC FOIT OII ('3 F C F: Substance (B): CFa-C F-C Fz-fJ-CII OII 3 C F3 0 F3 0 F3 C F3 Substance (C): C F3C FCF(|3 F-Oll OII I )5 0 F3 0 F3 A 200-cc., 4-necketl flask with a refluxcooler, thermometer, nitrogen gas injector, dropping funnel and agitatorwas charged with 86 grams of C F3 0 Fa C Fs-0 FCHO F-CHzOII f5 0 F; 0 Fasynthesized as above and 0.2 gram of hydroquinone and the mixture washeated with agitation at 7080 C. in a nitrogen gas stream, during which20 grams of methacryl chloride was added dropwise in about 30 minutes,after which the reaction was continued for about 1 hour. The resultantreaction mixture was distilled under reduced pressure, yielding 82.5grams of a distillate boiling at 8889 C./ 0.92 mm. Hg. The distillateshowed by infrared spectroscopic analysis absorptions at 5.75 due toC=O, at 6.15, due to and widely at 7-9.5;1. due to CF, and by elementaryanalysis the following values were found: C=31.5%; F=61.0%; H=1.50%.

Calculated values for C F H O C=30.5%; F: 62.18%; H=1.45%.

Thus the distillate was confirmed to be an ester of the startingfluorinated alcohol and methacrylchloride, i.e.,

and 450 grams of trichlorotrifluoroethane were placed in a 500-cc.,4-necked flask with a reflux cooler, thermometer, dropping funnel andnitrogen gas injector and the mixture was agitated in a nitrogen gasstream, and subjected to inrradiation of 400-watt ultra-violet rays at adistance of 45 cm. from the center of the flsk. During the irradiationtrichlorotrifiuoroethane partly vaporized away due to the radiant heatso trichlorotrifiuoroethane was added dropwise through the droppingfunnel as required. After 25 hours of irradiation 487 grams of a polymersolution of somewhat high viscosity, light yellow in color was obtained.The polymer concentration thereof was 9.5 Weight percent.

A part of said solution was diluted with trichlorotrifiuoroethane to apolymer concentration of 1.1 weight percent, in which the cuttings oftetron-cotton (65:35) cloth were dipped and lightly squeezed then dried.The cloth thus treated exhibited excellent oil-repellency, sustainingdrops of n-octane, machine oil, kerosene oil and frying oil for a longtime without infiltration.

EXAMPLE 3 150 grams of O F3 0 F3(|3 FC F=C FC Fa (boiling point, 46 C.),which were obtained in the manner as Example 1, and were separated froman isomer by repeated rectification, 46 grams of ethanol and 1.8 gramsof benzoyl peroxide were placed in a 200-cc. stainless steel autoclaveand the mixture was cooled with a Dry Icemethanol refrigerant and theair in the autoclave was thoroughly replaced by nitrogen gas. The systemwas then violently shaken at 100-108 C. for 10 hours. The resultantmixture was distilled to produce 107 grams of a distillate boiling at84-86 C./81 mm. Hg with 61 grams of the unreacted dimer recovered.

The distillate showed by infrared spectroscopic analysis a broadabsorption at 3.05, due to OH, a sharp one at 3.46;. due to CH and abroad one near 7-10p. due to CF, and was confirmed to be an additionproduct of ethanol and the starting dimer. By elementary analysis werefound: C=28.l%; F=64.3%; H=l.79%.

Calculated values for C F H O: C=27.8%; F: 65.8%; H=l.73%.

Further by nuclear magnetic resonance absorption analysis saiddistillate was confirmed to be:

100 grams of the fluorinated alcohol thus obtained, 0.3 gram ofhydroquinone, 83 grams of acrylic acid, 1 gram of cone. sulfuric acidand 200 cc. of carbon tetrachloride were placed in a SOD-cc. flaskequipped with a Soxhlets extractor and cooler, and the mixture washeated to a reflux temperature and maintained for 10 hours. During thereaction water produced was removed from an azeotropie mixture withcarbon tetrachloride by means of calcium carbonate placed in theextractor. After completion of the reaction carbon tetrachloride wasdistilled away and the residue to which 0.2 gram of hydroquinone wasfurther added was distilled under reduced pressure to obtaine 84 gramsof a distillate boiling at 90-91 C./ mm. Hg with 40 grams of unreactedacrylic acid recovered.

The distillate showed by infrared spectroscopic analysis absorptions at5.75 due to C=O and 6.15 due to HC:CH2.

Elementary analysis gave-Found: C=33.5%;

F=55.5%; H:2.2%. Calcd.: C=33.0%; F=57.0%;

(C F H O Thus the substance was confirmed to be obtained as above, 180grams of deoxidated water, 14 grams of acetone and 6.5 grams of NonionHS240 (trade mark for a polyoxyethylene alkyl phenol ether of NipponOils & Fats Co., Ltd., Japan) were placed in a 500-cc., 4-necked flaskwith a reflux cooler, thermometer, dropping funnel, nitrogen gasinjector and agitator, and the air in the flask was replaced by nitrogengas with thorough agitation, after which the temperature was graduallyraised with slow agitation to about 50 C., at which 100 grams of a 1.5weight percent of aqueous solution of potassium persulfate was addedthereto. Agitation was further continued at 51-57 C. for 4 hours and 30minutes, whereby 323 grams of a polymer dispersion of a concentration of8.7 weight percent, fluorescent in color and highly stable, wasobtained.

110 grams of said polymer dispersion, 40 cc. of isobutanol, 1 gram ofScoarol #100 (trademark for a nonionic surfactant (polyoxyethylenelauryl ether), of Kao Soap Co., Ltd., Japan), 890 grams of deionizedwater, 3 grams of sodium acetate, and 2.5 grams of acetic acid weremixed to constitute the first bath.

Further, 60 grams of Zeran AP (trademark for a water-repellent of DuPont de Nemours & Co., U.S.A.), 10 grams of Sumitex Resin M-3 (trademarkfor a synthetic resin of Sumitomo Chemical Co., Ltd., Japan), 1 gram ofSumitex ACX (trademark for a hardener of Sumitomo Chemical Co., Ltd.,Japan), 12 grams of sodium acetate and 1,000 grams of deionized waterwere tings were dipped in the first bath for 3 minutes, then lightlysqueezed, predried at -83" C. for 7 minutes and then cured at C. for 3minutes. The cuttings so treated were soaped for 1 minute at 45 '55 C.with a 0.3 weight percent aqueous solution of a neutral detergent and0.2 weight percent of soda ash, then thoroughly dried and dipped in thesecond bath, followed by drying and soaping in the similar manner, andfinally thoroughly washed with water and dried. The cotton poplin sotreated gave a refreshing touch, showing no noticeable decline instrength, and exhibited an excellent water-repellency andoil-repellency, showing 100 marks by AATCC spray test, as well assustaining without infiltration drops of a 20:80 volume ratio mixture ofliquid paraifin and n-heptane.

The cotton poplin treated as above exhibited exceedingly excellentresistance to washing. For instance, its waterand oil-repellency showedno noticeable change after repetition of 5 cycles of washing by ahousehold washing machine in which a 0.5 weight percent aqueous solutionof a neutral detergent was used.

EXAMPLE 4 300 grams of a mixture of 2 species of hexafluoropropylenedimers same as those employed in Example 1, 180 grams of anhydrousisopropanol, 200 grams of trifiuorotrichloroethane, and 10 grams ofazobisisobutyronitrile were placed in a 500-cc. autoclave, and the airin the autoclave was replaced by nitrogen gas. Thereafter the mixturewas heated with violent shaking at 80 C. for 26 hours. The repeatedfractional distillation of the resultant reaction mixture gave 106 gramsof a distillate (A) boiling at 77-80 C./50-52 mm. Hg and 73 grams of adistillate (B) boiling at 72-74 C./50-51 mm. Hg.

These substances (A) and (B) above were confirmed respectively to be afluorinated alcohol by infrared spectroscopic analysis, and further bymeasuring molecular weights thereof using difluorotetrachloroethane thefollowing results were obtained.-Found: Substance (A)=358; Substance(B)=353. Calcd.: 360 (C F H O).

From the above finding, the above substances were confirmed respectivelyto be an addition products of isopropyl alcohol to the starting dimer,and further by nuclear magnetic resonance absorption analysis wasconfirmed that Compound (A) was was esterified with acrylchloride in thesame manner as Example I, and by rectification of the resultant mixture95 grams of a distillate boiling at 9697 C./20 mm. Hg was obtained. Thiscompound was confirmed by infrared spectroscopic analysis to be afluorinated ester having a double-bond, and further by elementaryanalysis were found: C=33.2%; F=54.8%; H=2.5%.

Calculated values for C F H O F=55.0%; H=2.4%.

Thus the compound was comfirmed to be an ester of acrylic acid and saidalcohol.

thus obtained 800 grams of deoxidated water and 4 grams of CF (CF COONHwere placed in a 1-liter stainless steel autoclave, and the air in theautoclave was thoroughly replaced by nitrogen gas. Thereafter system wasslowly agitated at room temperature and subjected to irradiation of'y-rays emitting from 2,000-curie Co source at a dose rate of 7.5)(10r./ hr. for 1 hour. There occured no changes in the reaction temperatureand pressure, maintaining 23.5 C. and kg./ :m. G. Agitation continuedfor 40 minutes after completion of the irradiation, whereby 880 grams ofa polymer dispersion having a concentration of 9.8 weight percent,opaque and milk white in color was obtained. The dispersion was sostable that no precipitate was produced after lapse of 6 months.

Woolen gabardine cuttings treated with polymer dispersion thus obtainedin the same manner as Example 1 exhibited excellent waterandoil-repellency.

What is claimed is:

1. A fluorocarbon compound having the formula:

wherein R RE, RE and R are respectively one member of the groupconsisting of -F, -CF -CF CF /C F3 CF /C Fa C F a --OF OF and GFCF CF;CF; with the proviso that R and R are not both -F and RE and Rf are notboth F; R, R and R are respectively one member of the group consistingof H and -CH and n is an integer of from 0 to 10.

2. The fluorocarbon compound of claim 1 in which n is an integer ofzero.

3. The fluorocarbon compound of claim 1, in which both R and R arehydrogen and n is an integer of zero.

4. A polymer having a skeletal chain containing ester units representedby the formula:

wherein R}, R3, RR and Rf are respectively one member of the groupconsisting of F, -CF CF CF /G F3 /GF3 -CF -C F CF and r CFCFrespectively, with the proviso that R and R3 are not both -F and R9 andR; are not both -F; R R and R are respectively one member of the groupconsisting of -H and -CH and n is an integer from 0 to 10.

5. An article which is coated with the polymer specified in claim 4.

References Cited UNITED STATES PATENTS 3,025,279 3/1962 Barr 260-86.13,177,185 4/1965 Hollander et al. 3,249,596 5/1966 Pierce et a1. 260-861HARRY WONG, 111., Primary Examiner US. Cl. X.R.

Ill-161, 140, 155, 145, 138.8, 142, 124-, 148; 204-15922; 260-486, 86.1,63, 86.7, 86.3, 83.5, 29.6. 32.8, 33.8. 89.3

